Cant say for sure but I would think that hydronation of Pyridine with Na/EtOH to piperdine then oxidation to the ketone could get you there. Just a thought I have never really researched it alot

Which piperidone are you talking about? Considering the unsubstituted parent compound, I can think of 3 isomers (i.e. piperidin-2-one, -3-one & -4-one).


Piperidin-2-one (a.k.a. ?-valerolactame)
Preparative approaches
- Beckmann-rearrangement of cyclopentanone oxime: Lett Org Chem 2008, 5(6), p.495
- Beckmann-rearrangement of cyclopentanone, employing ammonium sulfate in sulfuric acid: US 2579851 (1951); 98% yield according to the patent!
- reaction of ?-valerolactone in liquid ammonia @230°C (ummm, tasty!): JACS 1952, 74, p.2012
- Beckmann rearrangement of cyclopentanone oxime with thionylchloride in chloroform: J Chem Soc 1956, p.4694
Note 1: Cyclopentanone oxime can be prepared from cyclopentanone and hydroxyl amine hydrochloride in almost quantitative yield.
- cyclization of 5-chlorovaleramides in EtOH: Chem Ber 1967, 100(6), p.2122
- cyclization of 5-chlorovalerianic acid in liquid ammonia in an autoclave at 250°C: Zhurnal Obshchei Khimii 1957, 27, p.2418; yield reported = 93%
Note 2: The Beckmann rearrangement seems to be to by far most usual route to this compound and several procedures are published. I think some of them are available in standard textbooks on this topic, although I haven't looked for them. My recommendation: "Vogel's Textbook of Practical Organic Chemistry", or the "Organikum" for german readers.


Piperidin-3-one
This compound is - in contrary to the first mentioned one - by far less common, and while there are dozens of preparations published for piperidin-2-one, there are almost none for the 3-isomer. But "almost" doesn't mean "none".
WO 2004 000827 describes te following:

Cyclic ketones (e.g., tetrahydro-3-furanone) are prepd. in an industrially viable manner by the reaction of partially unsatd. substrates (e.g., 2,5-dihydrofuran) with N2O or its mixts. with an inert gas at 20-250/0.01-100 atm.

Not feasible for a home-based lab, I'm afraid...No idea about the yields, somebody has to check the patent. But SciFinder describes as products both the 3- & 4-one derivative.
It is also possible to get the desired piperidin-3-one by enzyme-assisted reaction of the corresponding piperidine-3-amine with ?-transaminases, as described in Adv Synth Catal 2008, 350(6), p.807.


Piperidin-4-one
This compound is commonly prepared by the following (general) route:
1: 4-Hydroxypyridine:
1a: Para-hydroxylation of pyridine is achieved by reacting plain pyridine with thionylchloride to 1-(4'-pyridyl)pyridinium, which can be hydrolyzed by water, to yield 4-hydroxypyridine. See e.g. J Chem Soc 1954, pp.1795-8.
1b: Diazotization, followed by replacement of p-amino-pyridine yields 4-hydroxy-pyridine. This takes already place at -15°C in acidic solution (H2SO4). Yields are almost quantitative.
1b: One prepares chelidamic acid (= 4-hydroxy-pyridin-2,6-dicarboxylic acid) by condensation of oxalic acid diethylester with acetone in presence of NaOEt and consecutive heating with ammonia. This is then thermally decarboxylized, yielding 4-hydroxy-pyridine.

2. 4-hydroxy-pyridine is then reduced to 4-hydroxy-piperidine (e.g. by Birch reduction or with hydrogen over ruthenium catalysts).

3. Finally, oxidation of the alcohol leads to the desired 4-oxo piperidine.


Peace! Murphy

Acetone? The proposed route doesn't use any acetone, but acetonedicarboxylic ester, which is the same as double-esterified 3-oxopentanedioic acid. I think the free acid won't work, because it forms salts with the amine-reagent.

I'm not familiar with this synth but it looks like it produces symmetric products only. So: No piperidin-3-one, just the 4-oxo derivatives.

Mr.Murphy

How? The ketone of piperidin-4-one is introduced via the employed ketone. The whole reaction is a 3+(2x1)+1 ring formation, the respective parts coming from the acetonedicarboxylic ester (3), the used aldehydes (2x1) and the primary amine (1). How do you introduce an oxo-group in position 3 by this method?

 

Murphy

Mannich condensation is suggested in this article. Perhaps between the flames.

2b

Oh there was no flaming at all! Flaming on my side would include at least once the usage of the word "fuck"...

We just cleared out some nomenclature issues.

- Murphy

Another idea is the addition of two methyl/ethyl acrylates to ammonia then sodium methoxide/ethoxide followed by treatment with acid. I had a paper for a reaction like this but I cant find it   ill post later if I can find it

Edit:
Heres one-
J. Am. Chem. Soc., 1931, 53 (7), pp 2692–2696

But of more interest would be this:

J. Am. Chem. Soc., 1946, 68 (6), pp 1049–1053

I am assuming you will probably be going to NPP so the second might be a little more in the direction you could go. Both use the methyl/ethyl acrylate but what I like about the second article is it works with the di, tri, and tertiary products to convert all to usable substances. might take a little more work but also a little for economical.

~Bass

I have the papers but just didn't feel like uploading them right then... or I guess ever. But it does look very very interesting if you can substitute the benzyl chloride for phenethyl chloride or something along those lines. Or maybe just starting with phenethyl amine instead of ammonia and go from there. 

@basstabone, sorry I thought considering you'd presented the reference openly, that putting up the paper would be fine, and thought you may not of had them, and only the references.  I actually pmd you and offered to delete, but it would now include others so I guess it stands..

@no1uno, that is interesting, the "here" link appears to be dead also,, Ill check out the copper nicotinate as that seems a better way to go if it works.. for the pyridine etc, still thinking about this paper some more.

http://www.dtic.mil/cgi-bin/GetTRDoc?AD=ADA250611&Location=U2&doc=GetTRDoc.pdf There it shows an outline from phenethyl amine. It seems like the most direct and easy route but I just cant find an references on any of the reactions that I have access to. Any help?